EP3988294A1 - Étiquettes gravables au laser - Google Patents

Étiquettes gravables au laser Download PDF

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Publication number
EP3988294A1
EP3988294A1 EP20203881.6A EP20203881A EP3988294A1 EP 3988294 A1 EP3988294 A1 EP 3988294A1 EP 20203881 A EP20203881 A EP 20203881A EP 3988294 A1 EP3988294 A1 EP 3988294A1
Authority
EP
European Patent Office
Prior art keywords
layer
acrylic
foil
coextruded
several
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20203881.6A
Other languages
German (de)
English (en)
Inventor
designation of the inventor has not yet been filed The
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Priority to EP20203881.6A priority Critical patent/EP3988294A1/fr
Priority to KR1020237017628A priority patent/KR20230093042A/ko
Priority to CN202180072822.9A priority patent/CN116390853A/zh
Priority to JP2023525072A priority patent/JP2023547629A/ja
Priority to IL302251A priority patent/IL302251A/en
Priority to PCT/EP2021/079197 priority patent/WO2022090048A1/fr
Priority to EP21791423.3A priority patent/EP4232276A1/fr
Priority to US18/249,483 priority patent/US20230391057A1/en
Publication of EP3988294A1 publication Critical patent/EP3988294A1/fr
Pending legal-status Critical Current

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Definitions

  • the present invention relates to coextruded acrylic foils made from impact-modified polyalkyl (meth)acrylates and laser engravable labels comprising these foils.
  • the coextruded acrylic foils are designed for labelling by means of a laser and comprise a contrast layer having at least one inorganic filler and an engraving layer arranged on the contrast layer and having at least one colourant.
  • the contrast layer and the engraving layer comprise one or several impact modifiers.
  • the laser engravable labels are rather brittle and therefore an unauthorised attempt to peel off the label from a substrate results in destruction of the label. Normally, the laser engravable labels have no intended break points such as slits, perforation etc.
  • the laser engravable labels of the present invention have a high softening temperature and an excellent weathering stability and, in particular, an outstanding UV stability.
  • the labels may also be designed to show an excellent chemical resistance in the presence of a variety of chemicals commonly used in the automotive area.
  • Such labels can be used in application at temperatures of more than 100 °C without showing any signs of shrinkage in any dimension.
  • Such applications include inter alia electronic product identification labels, labels for electronic modules such as chips, electric engines and light emitting devices, which are operated at increased temperatures, various automotive under-the-hood labels, road tax badges, document seals, labels for product theft prevention etc.
  • Laser engravable labels are gaining increasing importance in the area of electronics and automotive, for example as type plates, as control labels for process sequences and as warranty and test labels because they can be quickly engraved and attached to the substrate of interest in a fully automated manufacturing process. In many cases, these applications inherently require a more or less pronounced degree of protection against forgery.
  • the bonding strength of the label to a labelled substrate is high in comparison with the strength (flexural strength or tear strength) of the label itself. Therefore, ideally, such labels cannot be peeled off from the labelled article without destroying the label.
  • laser engravable labels With the help of laser engravable labels, technical information and instructions such as tire pressure or type of fuel are placed on various components of motor vehicles.
  • laser engravable labels can also contain safety information such as chassis and vehicle identification numbers, registration number etc.
  • Corresponding labels allow conclusions to be drawn about the vehicle and production stages in its manufacture in the event of theft, illegal dumping or accident.
  • Laser engravable labels which allow a high contrast of written characters are known from the prior art.
  • DE 81 30 861 U1 , DE 100 48 665 A1 and DE 101 42 638 A1 described multi-layer labels which contain a thin and a thick acrylate-based lacquer layer.
  • During manufacturing of these labels at least two differently coloured acrylate-based layers are coated on top of one another. Before each subsequent coating step, the previously coated layer is cured and thus serves as a solid substrate for the subsequent coating. Since the corresponding manufacturing process involves several subsequent steps of coating and curing, the entire procedure requires complex equipment and sufferers from a limited efficiency.
  • JP 2017-111344 A describes a laser engravable foil having a white layer and a back layer which can be made of various thermoplastic materials.
  • the method of manufacturing both layers of said foil is not particularly limited and may involve e.g. extrusion or solvent coating.
  • JP 2017-111344 A does not teach preparation of acrylic laser engravable foils by means of coextrusion.
  • WO 2019/057645 A1 describes laser engravable foils which can be manufactured by means of a coextrusion using a chill-roll process.
  • the foils comprise an acrylic contrast layer and an acrylic engraving layer arranged on the contrast layer and are reported to have only a low shrinkage at extended temperatures.
  • either the contrast layer or the engraving layer must necessarily be free from impact modifiers to ensure a sufficient degree of brittleness.
  • WO 2019/057645 A1 reports that the foil could be successfully coextruded using laboratory-scale equipment at an extrusion speed of 4 m/min.
  • laser engravable labels are typically manufactured from a label stock that comprises a face layer (facestock), an adhesive, e.g. a pressure-sensitive adhesive (PSA) layer adhered to the face layer, optionally, a release coating layer, and a support layer removably adhered to the adhesive layer or to the release coating layer.
  • the label stock is generally provided in form of a roll.
  • Individual laser engravable labels are usually produced by die cutting (kiss cutting) the face layer and the PSA layer, and then removing the surrounding waste matrix, leaving the individual labels adhered to the support layer. Since the material of the face layer is highly brittle, removal of the waste matrix becomes highly problematic since it can easily break or tear apart.
  • Typical manufacturing processes for labels are run at speeds of at least 25 m/min or even higher. As the speed increases, the process becomes less stable and risk that the waste matrix breaks or tears apart upon removal increases. Slowing the process down or increasing the web width of the waste matrix to allow a better removal of the waste matrix, however, would result in a significant cost disadvantage, loss of efficiency, and may frequently be ineffective.
  • the problem addressed by the present invention was provision of a laser engravable foil for use in laser engravable labels having a sufficient brittleness for forgery prevention applications.
  • a laser engravable foil for use in laser engravable labels having a sufficient brittleness for forgery prevention applications.
  • the desired foil should ideally show substantially no signs of shrinkage at increased temperatures.
  • laser engravable labels possess a sufficiently low initial tear strength, a low tear propagation resistance and a short tear path to facilitate a complete rupture of the foil during an attempt of its non-authorised removal but, nevertheless, can be produced and processed without tearing.
  • the present invention addressed the problem of providing self-adhesive laser engravable forgery prevention labels which can be manufactured in a highly efficient manner, are printable and suitable for a long-term outdoor use.
  • the present invention addressed the problem of developing a safe and a cost-efficient process for the manufacturing the laser engravable foil described above and the self-adhesive labels comprising the same.
  • the present invention is based on a surprising finding that mechanical stability of coextruded acrylic foils can be improved significantly by ensuring that at least the contrast layer and the engraving layer of the foil comprise at least one impact modifying agent. Because no acrylic layers having no impact modifiers are present, formation of undesired cracks propagating through the entire foil no longer takes place. Hence, coextrusion of the foil on an industrial scale at a high extrusion speed becomes possible. At the same time, brittleness of the laser engravable foil can be finely adjusted in order to prevent any unauthorised removal of the attached label from a substrate. Additionally, the inventors surprisingly found that the foils show an excellent behaviour during a die cutting (kiss cutting) process, followed by stripping of the waste matrix.
  • laser engravable labels comprising the foil of the present invention can be advantageously manufactured upon employing a step in which individual labels are produced by kiss cutting, and the surrounding waste matrix is subsequently removed, leaving the individual labels adhered to the support layer. No undesired breaking of the waste matrix takes place, even at running speeds of at least 25 m/min or even higher.
  • one aspect of the present invention relates to coextruded acrylic foil comprising a layer A and a layer B.
  • the layer A comprises:
  • the layer B comprises:
  • foil refers to a sheet having a thickness below 5 mm, more preferably, below 1 mm.
  • the term “ foil” as used in the present application should be generally distinguished from the term " coating " .
  • a coating is typically a top layer of a multi-layer substrate and cannot be handled separately from said substrate.
  • the foil of the present invention is not necessarily a layer of a multi-layer article i.e. is not necessarily attached to any substrate and can therefore be separately handled and used for a variety of different purposes.
  • a laminate for the manufacturing of said laser engraving label comprising at least the following layers:
  • Still a further aspect of the present invention relates to a process for the manufacturing of the laminate, the process comprising at least the following steps:
  • the present invention relates to use of the coextruded acrylic foil for the manufacturing of laser engravable labels.
  • the co-extruded acrylic foil 4 comprises the layer A 5 and the layer B 6.
  • the coextruded acrylic foil of the present invention comprises at least a layer A and a layer B, wherein the layer A comprises:
  • the layer B comprises:
  • the inventor surprisingly found that the behaviour of the coextruded acrylic foil during extrusion on industrial scale and during the die cutting (kiss cutting) process, followed by stripping of the waste matrix, strongly depends on the ratio between the impact modifier amount and the amount of the inorganic fillers and colourants in the layers A und B of the co-extruded foil.
  • n imA in the layer A is described by the following relationship: n fA + n pA ⁇ n imA ⁇ 7 * n fA + n pA preferably 1.2 * n fA + n pA ⁇ n imA ⁇ 6.5 * n fA + n pA more preferably 1.3 * n fA + n pA ⁇ n imA ⁇ 6 * n fA + n pA
  • n imB in the layer B it showed to be highly beneficial in terms of behaviour of the coextruded acrylic foil during extrusion on an industrial scale and during the die cutting (kiss cutting) process, to choose the content, in wt.-%, of one or several impact modifiers n imB in the layer B to be described by the following relationship: 0.25 * n fB ⁇ n imB ⁇ 2 * n fB preferably 0.3 * n fB ⁇ n imB ⁇ 1.8 * n fB more preferably 0.4 * n fB ⁇ n imB ⁇ 1.5 * n fB n fB being the content, in wt.-%, of one or several inorganic fillers in the layer B.
  • laser engravable labels comprising the foil of the present invention can be manufactured upon employing a step in which individual labels are produced by kiss cutting, and the surrounding waste matrix is subsequently removed, leaving the individual labels adhered to the support layer. No undesired breaking of the waste matrix takes place, even at running speeds of at least 25 m/min or even higher.
  • n im is the content of neat impact modifiers.
  • n im is the content of the rubbery particles.
  • n im is the content of the entire particles.
  • one embodiment of the present invention relates to a coextruded acrylic foil comprising at least a layer A and a layer B, wherein the layer A comprises:
  • a coextruded acrylic foil comprising at least a layer A and a layer B, wherein the layer A comprises:
  • the coextruded acrylic foil comprises at least a layer A and a layer B, wherein the layer A comprises:
  • Coextruded acrylic foils having a particularly low shrinkage at increased temperatures can be obtained if glass transition temperature of at least one of the acrylic polymers A and / or of at least one of the acrylic polymers B is at least 110 °C, preferably at least 120 °C.
  • glass transition temperature of at least one of the acrylic polymers A and / or of at least one of the acrylic polymers B is at least 110 °C, preferably at least 120 °C.
  • the entire acrylic foil has a low shrinkage at increased temperatures.
  • the layer having a higher glass transition temperature provides a sufficient mechanical support to the layer with the lower glass temperature thereby avoiding undesired shrinkage of the foil.
  • Glass transition temperature Tg of an acrylic polymer can be determined in a known manner by means of differential scanning calorimetry (DSC).
  • the DSC-measurements can e.g. be performed by an instrument DSC 822e obtainable from Mettler-Toledo AG according to the norm DIN EN ISO 11357. For this purpose, two cycles are performed within the interval between -80 °C and 150 °C.
  • the heating/cooling rate is preferably10 °C/min.
  • the glass transition temperature Tg can be typically calculated by using a half-height technique in the transition region.
  • the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation.
  • 1 Tg x 1 Tg 1 + x 2 Tg 2 + ... + x n Tg n
  • x n is the mass fraction (% by weight/100) of the monomer n
  • Tg n is the glass transition temperature in kelvin of the homopolymer of the monomer n.
  • the acrylic polymer A and / or the acrylic polymer B are independently a poly(meth)acrylimide (PMMI) comprising at least 50 wt.-%, preferably at least 60 wt.-%, most preferably at least 70 wt.-%, based on the weight of the PMMI, of repeating units of Formula (I)
  • PMMI poly(meth)acrylimide
  • the acrylic layer A and / or the acrylic layer B comprises from 30.0 wt.-% to 98.0 wt.-%, preferably from 30.0 wt.-% to 92.5 wt.-%, more preferably from 40.0 wt.-% to 80.0 wt.-%, even more preferably from 45.0 wt.-% to 75.0 wt.-% of PMMI, based on the weight of the corresponding layer A or layer B.
  • the starting material used for preparation of PMMI comprises a polymer derived from alkyl esters of methacrylic acid and generally composed of more than 50.0% by weight, preferably of more than 80.0% by weight, particularly preferably of from 95.0% by weight to 100.0% by weight, of units of alkyl esters of methacrylic acid having from 1 to 4 carbon atoms in the alkyl radical. Methyl methacrylate is preferred.
  • Preferred polymers are composed of at least 80.0% by weight, preferably of more than 90.0% by weight, particularly preferably of more than 95.0% by weight, of methyl methacrylate.
  • Comonomers that can be used comprise any of the monomers copolymerizable with methyl methacrylate, in particular alkyl esters of acrylic acid having from 1 to 4 carbon atoms in the alkyl radical, acrylo- or methacrylonitrile, acryl or methacrylamide, styrene, or else maleic anhydride.
  • thermoplastically processable polymers of this type whose reduced viscosity is in the range from 20 ml/g to 92 ml/g, preferably from 50 ml/g to 80 ml/g (measured to ISO 8257 (2006), Part 2). They are used in the form of powder or pellets whose median particle size is from about 0.03 mm to 3 mm.
  • ammonia is first used as imidating agent, and that, in a subsequent step of the process, a C 1-4 -alkylamine, typically methylamine is used, and that the molar ratio of ammonia used to the methylamine used is from 1 : 0.5 to 1 : 3, preferably from 1 : 0.8 to 1 : 2.7, particularly preferably from 1 : 0.9 to 1 : 1.1. Below this range, haze can occur to an increased extent in the polymethacrylimide obtained. If there is a molar excess of methylamine, based on the ammonia used, the proportion of carboxylic acid groups in the polymer in turn rises undesirably.
  • the reaction with the imidating agent is preferably terminated before the polymer has been completely imidated.
  • the total amount used of the imidating agents can, for example, be from 0.2 to 2.5 mol, preferably from 0.5 to 1.5 mol, particularly preferably from 0.8 to 1.2 mol, per underlying mol of the ester units.
  • the defined quantitative ratio of ammonia to methylamine is always to be maintained. This then gives polymers which are composed of from about 20 underlying mol% to 80 underlying mol% of cyclic methacrylimide units, and which have only small amounts, less than 5.0% by weight, of methacrylic acid units.
  • the imidation process can be carried out substantially in a manner known per se, e.g. as described in EP 441 148 .
  • the imidation proceeds best at temperatures above the melting point or at least 20°C above the Vicat B softening point to ISO 306 (2014) for the starting polymer. It is more preferable to select a reaction temperature which is at least 20 °C above the softening point of the resultant imidated polymer. Since the Vicat softening point of the imidated polymer is generally the target variable of the process, and the degree of imidation to be achieved is defined in accordance therewith, it is likewise readily possible to determine the required minimum temperature.
  • a temperature range of from 140 °C to 300 °C is preferred, in particular from 150 °C to 260 °C, particularly preferably from 180 °C to 220 °C.
  • reaction temperatures sometimes lead to a reduction in viscosity caused by some extent of chain termination of the polymer.
  • the reaction temperature can, for example, be raised gradually or in stages, starting from a temperature slightly above the melting point of the starting polymer, and only at a final juncture exceed the softening point of the imidated end product by at least 20 °C. Within the stages of the reaction, it is preferable to operate with autogenous pressure, which can be from 50 bar to 500 bar.
  • Depressurization can be carried out during the stages of the process, e.g. for devolatilization.
  • the temperature of the reaction mixture can fall here and must then be increased back to the required value. If imidating agent is introduced under reaction conditions, an appropriately high pressure must, of course, be used for this purpose.
  • Partial or complete imidation of polymers of alkyl esters of methacrylic acid via reaction with an imidating agent, for example with a primary amine, is disclosed by way of example in US 2.146.209 .
  • the polymer is heated to temperatures of from 140 °C to 250 °C in the presence or absence of a solvent with the imidating agent, if appropriate under pressure.
  • PMMIs for use in the present invention have a mass average molar weight Mw of from 80 000 g/mol to 200 000 g/mol, preferably from 90 000 g/mol to 150 000 g/mol, determined by GPC using PMMA as a standard.
  • Such materials are commercially available from Röhm GmbH (Darmstadt, Germany) under the trademark PLEXIMID ® .
  • Suitable products include but are not limited to PLEXIMID ® TT50, PLEXIMID ® TT70, PLEXIMID ® 8805, PLEXIMID ® 8813, PLEXIMID ® 8817.
  • the acrylic polymer A and / or the acrylic polymer B are independently polyalkyl(meth)acrylates.
  • Polyalkyl(meth)acrylates are usually obtained by free-radical polymerization of mixtures which typically comprise an alkyl(meth)acrylate, typically methyl methacrylate (a), and at least one further (meth)acrylate (b). These mixtures generally comprise at least 50 wt.-%, preferably at least 60 wt.-%, particularly preferably at least 80 wt.-%, and even more preferably at least 90 wt.-%, based on the weight of the monomers, of methyl methacrylate (a).
  • the amount of methyl methacrylate (a) generally used is from 50.0 wt.-% to 99.9 wt.-%, preferably from 80.0 wt.-% to 99.0 wt.-% and particularly preferably from 90.0 wt.-% to 99.0 wt.-%, based on the weight of monomers.
  • mixtures for production of polyalkyl(meth)acrylates can also comprise other (meth)acrylates (b) copolymerizable with methyl methacrylate (a).
  • (meth)acrylate as used herein is meant to encompass methacrylates, acrylates and mixtures thereof.
  • (Meth)acrylates may derive from saturated alcohols, e.g.
  • the amount of the (meth)acrylic comonomers (b) generally used is from 0.1 wt.-% to 50.0 wt.-%, preferably from 1.0 wt.-% to 20.0 wt.-% and particularly preferably from 1.0 wt.-% to 10.0 wt.-%, based on the weight of monomers, and the compounds here can be used individually or in the form of a mixture.
  • the polymerization reaction is generally initiated by known free-radical initiators.
  • the preferred initiators are inter alia the azo initiators well known to persons skilled in the art, e.g. AIBN and 1,1-azobiscyclohexanecarbonitrile, and peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert -butyl 2-ethylperhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert -butyl peroxybenzoate, tert -butylperoxy isopropyl carbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert -butyl 2-ethylperoxyhexanoate, tert -
  • compositions to be polymerized can comprise not only the methyl methacrylate (a) and the (meth)acrylates (b) described above but also other unsaturated monomers which are copolymerizable with methyl methacrylate and with the abovementioned (meth)acrylates.
  • 1-alkenes such as 1-hexene, 1-heptene
  • branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methyl-1-pentene, norbornene
  • acrylonitrile vinyl esters, such as vinyl acetate
  • styrene substituted styrenes having an alkyl substituent in the side chain, e.g. ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes having an alkyl substituent on the ring, e.g.
  • vinyltoluene and p -methylstyrene halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; vinyl ethers and isoprenyl ethers; maleic acid derivatives, such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide; and dienes, such as divinylbenzene.
  • the amount of these comonomers (c) generally used is from 0.0 wt.-% to 20.0 wt.-%, preferably from 0.0 wt.-% to 15.0 wt.-% and particularly preferably from 0.0 wt.-% to 10.0 wt.-%, based on the weight of monomers, and the compounds here can be used individually or in the form of a mixture.
  • polyalkyl(meth)acrylates which are obtainable by polymerization of a composition having, as polymerizable constituents:
  • polyalkyl(meth)acrylates composed of from 85.0 wt.-% to 99.5 wt.% of methyl methacrylate and from 0.5 wt.-% to 15.0 wt.-% of methyl acrylate, the amounts here being based on 100 wt.-% of the polymerizable constituents.
  • Particularly advantageous copolymers are those obtainable by copolymerization of from 90.0 wt.-% to 99.5 wt.-% of methyl methacrylate and from 0.5 wt.-% to 10.0 wt.-% of methyl acrylate, where the amounts are based on 100 wt.-% of the polymerizable constituents.
  • the polyalkyl(meth)acrylates may comprise 91.0 wt.-% of methyl methacrylate and 9.0 wt.-% of methyl acrylate, 96.0 wt.-% of methyl methacrylate and 4.0 wt.-% of methyl acrylate or 99.0 wt.-% of methyl methacrylate and 1.0 wt.-% of methyl acrylate.
  • the Vicat softening points VSP (ISO 306 (2013), method B50) of said polyalkyl(meth)acrylates is typically at least 90 °C, preferably from 95 °C to 112 °C.
  • the weight-average molar mass Mw of the polyalkyl(meth)acrylates is generally in the range from 80 000 g/mol to 300 000 g/mol.
  • Particularly advantageous mechanical properties are obtained from foils with polyalkyl(meth)acrylates having an average molar mass Mw in the range from 80 000 g/mol to 200 000 g/mol, preferably in the range from 100 000 g/molto 180 000 g/mol, more preferably in the range from 120 000 g/molto 180 000 g/mol, in each case determined by means of GPC against PMMA calibration standards and THF as an eluent.
  • Suitable polyalkyl(meth)acrylates for use in the foils of the present invention are commercially available from Röhm GmbH (Darmstadt, Germany) under the trademark PLEXIGLAS ® .
  • Such products include but are not limited to PLEXIGLAS ® 7N, PLEXIGLAS ® 7H, PLEXIGLAS ® 8N, PLEXIGLAS ® 8H and PLEXIGLAS ® Heatresist FT15.
  • the foil of the present invention typically comprises from 0.0 wt.-% to 30.0 wt.-%, preferably from 0.0 wt.-% to 25.0 wt.-%, more preferably from 0.0 wt.-% to 20.0 wt.-% of a polyalkyl(meth)acrylate, based on the weight of the coextruded acrylic foil.
  • Impact modifiers for use in the present invention per se are well known and may have different chemical compositions and different polymer architectures.
  • the impact modifiers may be crosslinked or thermoplastic.
  • the impact modifiers may be in particulate form, as core-shell, as core-shell-shell or core-shell-shell-shell particles.
  • particulate impact modifiers have an average particle diameter between 20 nm and 500 nm, preferably between 50 nm and 450 nm, more preferably between 100 nm and 400 nm and most preferably between 150 nm and 350 nm.
  • Particulate in this context means crosslinked impact modifiers which generally have a core-shell, core-shell-shell or core-shell-shell-shell structure. Average particle diameter can be determined by a method known to a skilled person, e.g. by photon correlation spectroscopy according to the norm DIN ISO 13321 (2004).
  • particulate impact modifiers are crosslinked particles obtained by means of emulsion polymerization whose average particle diameter is in the range from 10 nm to 150 nm, preferably from 20 nm to 100 nm, in particular from 30 nm to 90 nm.
  • These are generally composed of at least 20.0 wt.-%, preferably from 20.0 wt.-% to 99.0 wt.-%, particularly preferably in the range from 30.0 wt.-% to 98.0 wt.-% of butyl acrylate, and from 0.1 wt.-% to 2.0 wt.-%, preferably from 0.5 wt.-% to 1.0 wt.-% of a crosslinking monomer, e.g. a polyfunctional (meth)acrylate, e.g. allyl methacrylate and, if appropriate, other monomers, e.g.
  • a crosslinking monomer e.g. a polyfunctional (meth)acrylate, e.g. allyl methacrylate and, if appropriate, other monomers, e.g.
  • C 1 -C 4 -alkyl methacrylates such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other vinylically polymerizable monomers, e.g. styrene.
  • Preferred impact modifiers are polymeric particles which can have a two- or three-layer core-shell structure and are obtained by emulsion polymerization (see, for example, EP-A 0 113 924 , EP-A 0 522 351 , EP-A 0 465 049 and EP-A 0 683 028 ).
  • the foils of present invention typically require suitable average particle diameter of these emulsion polymers in the range from 20 nm and 500 nm, preferably between 50 nm and 450 nm, more preferably between 100 nm and 400 nm and most preferably between 150 nm and 350 nm.
  • a three-layer or three-phase structure with a core and two shells can prepared as follows.
  • the innermost (hard) shell can, for example, be composed in essence of methyl methacrylate, of small proportions of comonomers, e.g. ethyl acrylate, and of a proportion of crosslinking agent, e.g. allyl methacrylate.
  • the middle (soft) shell can, for example, be composed of a copolymer comprising butyl acrylate and, if appropriate, styrene, while the outermost (hard) shell is in essence the same as the matrix polymer, thus bringing about compatibility and good linkage to the matrix.
  • the proportion of polybutyl acrylate in the core or in the shell of the impact modifier of a two- or three-layer core-shell structure is decisive for the impact-modifying action and is preferably in the range from 20.0 wt.-% to 99.0 wt.-%, particularly preferably in the range from 30.0 wt.-% to 98.0 wt.-%, even more preferably in the range from 40.0 wt.-% to 97.0 wt.-%, based on the total weight of the impact modifier.
  • particulate impact modifiers comprising copolymers of butyl acrylate
  • use of impact modifiers comprising siloxanes is also possible.
  • use of such modifiers is less advantageous, because their presence in the coextruded acrylic foil tends to be disadvantageous for printability of the foil.
  • Methyl methacrylate-butadiene-styrene (MBS) core-shell impact modifiers are also highly suitable for use in the foil of the present invention because of their excellent compatibility with PMMI.
  • the corresponding impact modifiers are commercially available from several manufacturers such as Arkema France under the trademark Clearstrength ® and include products such as Clearstrength ® XT100, Clearstrength ® 140, Clearstrength ® 223, Clearstrength ® 303H, Clearstrength ® 320, Clearstrength ® 350, Clearstrength ® 859.
  • MBS core-shell impact modifiers manufactured by The Dow Chemical Company under the trademark PARALOlD TM , for instance products PARALOID TM EXL-2620, PARALOID TM EXL TM 2650J, PARALOID TM EXL-2690, PARALOID TM EXL-2691, PARALOID TM EXL-2668 and PARALOID TM EXL-3361.
  • PARALOlD TM for instance products PARALOID TM EXL-2620, PARALOID TM EXL TM 2650J, PARALOID TM EXL-2690, PARALOID TM EXL-2691, PARALOID TM EXL-2668 and PARALOID TM EXL-3361.
  • PARALOlD TM for instance products PARALOID TM EXL-2620, PARALOID TM EXL TM 2650J, PARALOID TM EXL-2690, PARALO
  • core-shell-shell-shell impact modifier is advantageous in terms of mechanical properties of the foils of the present invention.
  • the corresponding impact modifiers are described in detail in the patent application WO 2014/035608 A1 , the entire disclosure of which is incorporated herein by reference.
  • Thermoplastic impact modifiers have a different mechanism of action than particulate impact modifiers. They are generally mixed with the matrix material.
  • preferred sizes for these domains the size of which can be determined, for example, by electron microscopy, correspond to preferred sizes for the core-shell particles.
  • thermoplastic impact modifiers There are various classes of thermoplastic impact modifiers.
  • One example thereof are aliphatic TPUs (thermoplastic polyurethanes) e.g. Desmopan ® products commercially available from Covestro AG.
  • TPUs Desmopan ® WDP 85784A, WDP 85092A, WDP 89085A and WDP 89051D are particularly suitable as impact modifiers.
  • thermoplastic polymers suitable for use in the foil of the present invention as impact modifiers are methacrylate-acrylate block copolymers, especially acrylic TPE, which comprises PMMA-poly- n -butyl acrylate-PMMA triblock copolymers, and which are commercially available under the Kurarity ® product name by Kuraray.
  • the poly- n -butyl acrylate blocks form nanodomains in the polymer matrix having a size between 10 nm and 20 nm.
  • thermoplastic impact modifiers comprising PVDF are also possible.
  • use of such modifiers is less advantageous, because their presence in the coextruded acrylic foil tends to worsen printability of the foil.
  • the cumulative content of the poly(meth)acrylimides, polyalkyl(meth)acrylates and the impact modifiers in the layer A (hereinafter referred to as " impact-modified acrylic polymers A ”) is usually adjusted to be from 60 wt.-% to 99.5 wt.-%, more preferably from 70.0 wt.-% to 98.0 wt.-%, more preferably from 80.0 wt.-% to 96.0 wt.-%, based on the weight of the layer A.
  • the cumulative content of the poly(meth)acrylimides, polyalkyl(meth)acrylates and the impact modifiers in the layer B (hereinafter referred to as " impact-modified acrylic polymers B ") is usually adjusted to be from 60 wt.-% to 95.0 wt.-%, more preferably from 65.0 wt.-% to 95.0 wt.-%, more preferably from 70.0 wt.-% to 90.0 wt.-%, based on the weight of the layer B.
  • Presence of inorganic fillers in the coextruded acrylic foil of the present invention serves several purposes. Presence of inorganic fillers allows rendering the coextruded acrylic foil to have a desired colour and degree of transparency. For instance, presence of titanium dioxide in the coextruded acrylic foil renders the foil white and substantially non-transparent. Additionally, the amount of inorganic filler was surprisingly found to have a strong effect on the foil behaviour during its handling, in particular, on behaviours of the foil during coextrusion on industrial scale and behaviour of the waste matrix after the kiss cutting step during manufacturing of laser engravable labels.
  • Inorganic fillers in the layers A and B are not particularly limited and can be independently selected from zirconium dioxide, titanium dioxide, preferably rutile-type titanium dioxide, silica, preferably fused silica, barium sulphate, aluminium trihydroxide, mica, zinc oxide, zinc sulphide, clay, muscovite and calcium carbonate.
  • the inorganic fillers show a 45 ⁇ m screen residue of not more than 0.1 wt.-%, i.e. substantially no agglomerates with a particle size larger than 45 ⁇ m are present, which is highly advantageous for use according to the present invention.
  • This allows the inorganic filler to be distributed in the matrix of poly(meth)acrylate foil in a particularly homogeneous manner without large filler agglomerates being present so that the resulting foil shows a substantially uniform visual appearance and has appropriate mechanical properties.
  • the presence of substantial amounts of larger filler agglomerates in the foil is disadvantageous, since such agglomerates tend to initiate foil cracks thereby reducing the initial tear strength at a random position of the foil.
  • the inorganic fillers have a weight-average particle diameter d 50 ranging between 0.05 ⁇ m and 10.0 ⁇ m, more preferably between 0.1 ⁇ m and 5.0 ⁇ m, particularly preferably between 0.1 ⁇ m and 1.0 ⁇ m, even more preferably between 0.1 ⁇ m and 0.5 ⁇ m.
  • the weight-average particle diameter d 50 can be determined by an appropriate method known to a skilled person, e.g.
  • the oil absorption of the inorganic filler is not less than 5 g/100 g filler, preferably not less than 10 g/100 g filler and particularly preferably not less than 15 g/100 g filler. It is further beneficial that the oil absorption of the inorganic filler is not more than 100 g/100 g filler, preferably not more than 70 g/100 g filler and particularly preferably not more than 50 g/100 g filler.
  • the oil absorption can be determined according to the norm DIN EN ISO 787-5 (1995).
  • titanium dioxide can be favourably employed as a filler.
  • titanium dioxide in form of rutile or anatase may be used, whereby titanium dioxide in form of rutile is particularly preferred due to its low photocatalytic activity.
  • Such materials can be manufactured by chloride process and are commercially available from various suppliers such as e.g. KRONOS TITAN GmbH (Leverkusen, Germany).
  • Suitable titanium dioxide fillers may be with or without modifications with water-insoluble oxides of aluminium, silicon, zinc, or other agents; these reagent materials are introduced specifically to improve those properties for which the colourant is used.
  • the titanium dioxide fillers should ideally be free of extenders such as barium sulphate, clay, magnesium silicate, whiting, etc. Particularly preferred are titanium dioxide fillers of types II, III and IV according to the classification ASTM D476 (2015).
  • the layer B usually comprises from 5.0 wt.-% to 35.0 wt.-%, preferably from 7.5 wt.-% to 32.5 wt.-%, more preferably from 10.0 wt.-% to 30.0 wt.-%, based on the weight of the layer B.
  • Colourants for use in the layer A of the foil are not particularly limited.
  • the colourant is a pigment.
  • the layer A of the films can be coloured in black.
  • Suitable pigments for this purpose can, for instance, the selected from carbon black, iron oxide, particularly iron (III) oxide, cobalt oxide, aniline black and perylene black, carbon black being particularly suitable.
  • a red coloured the layer A can be prepared by using at least one red pigments.
  • Suitable red pigments include but are not limited to (colour index C.I.) Pigment Red (PR) 48:2, 48:3, 57:1, 101, 112, 122, 144, 166, 168, 178, 179, 202, 214, 254, 255, 264, 272, 276, 277 and Pigment Violet (PV) 19.
  • colour index C.I. Pigment Red (PR) 48:2, 48:3, 57:1, 101, 112, 122, 144, 166, 168, 178, 179, 202, 214, 254, 255, 264, 272, 276, 277 and Pigment Violet (PV) 19.
  • the concentration of the pigment in the layer A mainly depends on the desired L*- value in CIELAB 1976 colour space.
  • the concentration is generally in the range from 0.5 to 20.0 wt.-% preferably from 1.0 to 10.0 wt.-%, more preferably from 1.5 to 7.0 wt.-%, based on the weight of the layer A.
  • Average primary particle size of carbon black pigment is normally in the range from 5.0 to 100.0 nm, more preferably from 7.0 to 60.0 nm.
  • Average particle size d 50 can be determined by a method known to a skilled person, e.g. by photon correlation spectroscopy according to the standard DIN ISO 13320 (2004) upon using a commercially available instrument such as LS 13 320 Laser Diffraction Particle Size Analyzer from Beckman Coulter Inc. It further showed to be advantageous in terms properties of the foil to select carbon black particles having a specific surface area, measured by BET method, standard ISO 9277, of from 50 to 500 m 2 / g, for instance from 70 to 400 m 2 / g.
  • the carbon black can be treated or untreated.
  • the carbon black can be treated with specific gases or organic substances, such as, for example, butyllithium. Such treatment allows the surface to be modified or functionalised. This can additionally promote compatibility with the polymeric matrix of the layer A.
  • Carbon blacks suitable for use of the foil of the present invention differ from so-called conductive blacks in that they have only low or no electrical conductivity. Compared with the carbon blacks used here, conductive blacks have specific morphologies and superlattices in order to achieve high conductivity. By contrast, carbon black particles used here can very readily be dispersed in thermoplastics so that virtually no cohesive regions of carbon black occur, from which a corresponding conductivity might result. Suitable carbon blacks are obtainable commercially under a large number of trade names and in a large number of forms, such as pellets or powder.
  • suitable carbon blacks are obtainable under the trade names BLACK PEARLS ® , in the form of wet-processed pellets under the names ELFTEX ® , REGAL ® and CSX ® , and in a flocculent form under the names MONARCH ® , ELFTEX ® , REGAL ® and MOGUL ® -all obtainable from Cabot Corporation.
  • Printex ® 60, and Printex ® 90 are also suitable for this purpose.
  • the colourant in the layer A is a dye.
  • Suitable dyes include in particular red dyes i.e. those designated as Solvent Red, Acid Red or Modern Red according to the colouring index (C.I.). Examples thereof include anthraquinone dyes such as Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; perinone dyes such as Solvent Red 135, 162, 179; as well as monoazo dyes such as Solvent Red 195.
  • UV absorbers and UV stabilizers for use in the foil of the present invention are well known and described in detail by way of example in Hans Zweifel, Plastics Additives Handbook, Hanser Verlag, 5th Edition, 2001, p. 141 ff .
  • UV stabilizers are understood to include UV stabilizers and free-radical scavengers.
  • UV absorbers can by way of example derive from the group of the substituted benzophenones, salicylic esters, cinnamic esters, oxanilides, benzoxazinones, hydroxyphenylbenzotriazoles, triazines or benzylidenemalonate.
  • the best-known representatives of the UV stabilizers/free-radical scavengers are provided by the group of the sterically hindered amines (hindered amine light stabilizer, HALS).
  • the combination of UV absorbers and UV stabilizers as used in the coextruded acrylic foil is composed of the following components:
  • the individual components can be used in the form of an individual substance or in a mixture.
  • Benzotriazole type UV absorbers are known in the prior art and are typically 2-(2'-hydroxyphenyl)benzotriazoles.
  • the corresponding compounds include in particular 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-di- tert -butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'- tert -butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert -butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'- tert -butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-(3'- sec -butyl-5'- tert -but
  • UV absorbers of benzotriazole type that can be used are 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3,5-di( ⁇ , ⁇ -dimethylbenzyl)phenyl]benzotriazole, 2-(2-hydroxy-3,5-di- tert- butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di- tert -butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di- tert- amylphenyl)benzotriazole, 2-(2-hydroxy-5- tert -butylphenyl)benzotriazole, 2-(2-hydroxy-3-sec-butyl-5- tert -butylphenyl)benzotriazole and 2-(2-hydroxy-5- tert -oct
  • Tinuvin ® 360 Tinuvin ® 234.
  • the amounts used of the UV absorbers of benzotriazole type are from 0.1 wt.-% to 5.0 wt.-%, preferably from 0.2 wt.-% to 3.0 wt.-% and very particularly preferably from 0.5 wt.-% to 2.0 wt.-%, based on the weight of the coextruded acrylic foil. It is also possible to use mixtures of different UV absorbers of benzotriazole type.
  • Triazine type UV absorbers are typically 2-(2-hydroxyphenyl)-1,3,5-triazines.
  • 2-(2-hydroxyphenyl)-1,3,5-triazines include inter alia 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecy
  • Tinuvin ® 1600 Tinuvin ® 1577 or Tinuvin ® 1545.
  • the amounts of the triazine type UV absorber are from 0.1 to 5.0 wt.-%, preferably from 0.2 to 3.0 wt.-% and very particularly preferably from 0.5 to 2.0 wt.-%, based on the weight of the foil. It is also possible to use mixtures of different triazine type UV absorbers.
  • the foil of the present invention may further contain one or more UV stabilisers which typically act as antioxidants, radical scavengers, etc.
  • Particularly preferred UV stabilisers are sterically hindered phenols and HALS type additives.
  • HALS H indered A mine L ight S tabilizer
  • UV stabilizers are per se known. They can be used to inhibit ageing phenomena in paints and plastics, especially in polyolefin plastics ( Kunststoffe, 74 (1984) 10, pp. 620-623 ; Park + Lack, Volume 96, 9/1990, pp. 689-693 ).
  • the tetramethylpiperidine group present in the HALS compounds is responsible for the stabilizing effect.
  • This class of compound can have no substitution on the piperidine nitrogen or else substitution by alkyl or acyl groups on the piperidine nitrogen.
  • the sterically hindered amines do not absorb in the UV region.
  • HALS compounds which have stabilizing effect and which can also be used in the form of mixtures are: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)-decane-2,5-dione, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, poly( N - ⁇ -hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine succinate) or bis( N -methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  • Tinuvin ® 123 Tinuvin ® 144 or Tinuvin ® 292.
  • the amounts used of the HALS compounds in the foil are typically from 0.0 to 5.0 wt.-%, preferably from 0.1 to 3.0 wt.-% and very particularly preferably from 0.2 to 2.0 wt.-%, based on the weight of the foil. It is also possible to use mixtures of different HALS compounds.
  • Sterically hindered phenols are also suitable for use in the foil of the present invention.
  • Preferred sterically hindered phenols include inter alia 6- tert -butyl-3-methylphenyl derivatives, 2,6-di- tert- butyl- p -cresol, 2,6- tert -butyl-4-ethyl phenol, 2,2'-methylenebis-(4-ethyl-6- tert -butyl phenol), 4,4'-butylidenebis(6- tert -butyl- m -cresol), 4,4'-thiobis(6- tert -butyl- m -cresol), 4,4'-dihydroxy diphenyl cyclohexane, alkylated bisphenol, styrenated phenol, 2,6-di- tert -butyl-4-methyl phenol, n -octadecyl-3-(3',
  • sterically hindered phenols include Sumilizer TM BHT BP-76, WXR, GA-80 and BP-101 (Sumitomo Chemical, Osaka, Japan), Irganox ® 1076, 565, 1035, 1425WL, 3114, 1330 and 1010 (BASF SE, Ludwigshafen, Germany), MARK AO-50,-80, -30, -20, -330 and -60 (ADEKA Polymer Addtives, Mulhouse, France), and Tominox ® SS, TT (Mitsubishi Chemical Corporation, Yoshitomi, Japan).
  • the foil of the present invention usually comprises from 0.0 wt.-% to 5.0 wt.-%, of one or several UV-absorbers and from 0.0 wt.-% to 5.0 wt.-% of one or several UV-stabilizers, based on the weight of the coextruded acrylic foil.
  • the coextruded acrylic foil of the present invention preferably has tensile strength of from 20.0 MPa to 70.0 MPa, measured according to DIN EN ISO 527-3/2/100 (2003) with a foil having a thickness of 50.0 ⁇ m.
  • the foil having a tensile strength lower than 20.0 MPa still would be suitable for use according to the present invention, a great attention would need to be taken during its manufacturing and handling, since the foil can easily tear apart.
  • the coextruded acrylic foil of the present invention having tensile strength of more than 70.0 MPa is highly suitable for the manufacturing process of laser engravable labels, use of such labels could bear an increased risk that such label can be removed using a thin sharp blade (e.g. a razor blade) from the originally labelled substrate and subsequently re-attached onto a different substrate.
  • a thin sharp blade e.g. a razor blade
  • the initial tear resistance is preferably in the range of from 1.0 N to 15.0 N.
  • the tensile strength of the coextruded acrylic foil can be determined by a common method known to a skilled person such as the method described in the standard DIN EN ISO 527-3/2/100 (2003) and is typically measured in the direction of extrusion.
  • the coextruded acrylic foil has resistance to tear propagation, measured according to ASTM D1938 (2014 ) with a foil having a thickness of 50.0 ⁇ m, of from 0.01 N to 1.50 N, preferably from 0.1 N to 1.00 N.
  • the resistance to tear propagation is typically measured in the direction of extrusion.
  • the coextruded acrylic foil has elongation at break ranging between 0.5 % to 30%, measured according to DIN EN ISO 527-3/2/100 (2003) with a foil having a thickness of 50.0 ⁇ m, whereby elongation at break ranging between 2.0% to 20.0% is particularly advantageous in terms of handling.
  • the manufacturing process may need to be run at a lower speed.
  • the elongation at break exceeds 30.0%, brittleness of the foil tends to decrease. Therefore, during an attempt to remove the laser engravable label with a thin sharp blade a minor mechanical deformation of the foil may not necessarily lead to its complete rupture. This increases the risk that a skilled and experienced individual using a sufficiently thin and sharp tool may succeed in removing the laser engravable label from the original substrate (e.g.
  • a replaceable part for a vehicle engine in order to re-attach it to a different object (a non-genuine replaceable part).
  • the elongation at break of the coextruded acrylic foil can be measured by a common method known to a skilled person such as the one described in the standard DIN EN ISO 527-3/2/100 (2003).
  • the major influencing factors are the amounts of impact modifiers and inorganic fillers. More particularly, an increase in concentration of the impact modifiers also increases the elongation at break, and therefore smaller amounts of impact modifiers contribute to a low elongation at break in accordance with the invention.
  • the initial tear resistance of the coextruded acrylic foil is at least 10 times as high, preferably at least 50 times as high, even more preferably at least 100 times as high as resistance to tear propagation. This is particularly advantageous and ensures that even a minor foil rupture occurring during an unauthorised attempt to remove the laser engravable label from a substrate rapidly propagates through the entire label and results in a complete label destruction. This additionally reduces the risk of an unauthorised label removal.
  • the dimensional stability of an extruded foil of the present invention at 120 °C (60 minutes) is not higher than 0.7%, preferably not higher than 0.5% in the machine direction orientation (direction of extrusion) and not higher than 0.5%, preferably not higher than 0.3% in the transverse direction (direction perpendicular to the machine direction).
  • the dimensional stability can be measured according to the norm DIN EN ISO 11501 (2004) using a foil having a thickness of 50.0 ⁇ m. The measurements can be carried out at 120 °C over a period of 30 minutes.
  • the foil of the present invention has an excellent chemical resistance in the presence of common chemicals such as disinfectants, detergents and various fluids commonly used in road vehicles such as hydraulic fluid, engine oil etc. For this reason, the foils are highly suitable for use as automotive under-the-hood labels.
  • the thickness of the coextruded acrylic foil of the present invention is preferably in the range of 10.0 ⁇ m to 200.0 ⁇ m. When the thickness is below 10.0 ⁇ m, a great care should be taken during manufacturing and handling of the foil to avoid its rupture. On the other hand, when the foil thickness exceeds 200.0 ⁇ m, its mechanical stability is rather high and this, again, increases the risk that the foil does not break during an attempt of an unauthorised label removal. Additionally, a high foil thickness will result in a high thickness of the laser engravable label comprising the same, which may be disadvantageous for aesthetical or other reasons.
  • the thickness of the coextruded acrylic foil is preferably in the range of 30.0 ⁇ m to 90.0 ⁇ m, a range of 40.0 ⁇ m to 75.0 ⁇ m being even more preferred.
  • the layer A has a thickness d A of from 2 ⁇ m to 100 ⁇ m, preferably from 5 ⁇ m to 90 ⁇ m, more preferably from 10 ⁇ m to 80 ⁇ m.
  • the layer B has normally a thickness d B of from 5 ⁇ m to 100 ⁇ m, preferably from 10 ⁇ m to 90 ⁇ m, more preferably from 20 ⁇ m to 80 ⁇ m.
  • the thickness of the foil of the present invention and of its individual layers A and B can be determined by mechanical scanning according to the norm ISO 4593 (1993).
  • the thickness of the foil of the present invention is determined using photomicrographs obtained using a scanning electron microscope such as JEOL JSM-IT300 (commercially available from JEOL GmbH, Freising, Germany).
  • JEOL JSM-IT300 commercially available from JEOL GmbH, Freising, Germany.
  • the foil samples can be frozen in liquid nitrogen, mechanically broken and the freshly obtained surfaces are analysed.
  • the measurement can be carried out using the following parameters: Current source: variable flow of electrons from a tungsten filament (cathode) Vacuum system: rotary pump / oil diffusion pump X-Y-Z-rotation-tilt: totally motorized Working distance (WD): 5 to 70 mm (common: 10 mm) Sample rotation: 360° Sample tilting: - 5 to max. 90° (depending on WD) Magnification: 10 x to 300 000 x Maximum resolution: ⁇ 3 nm Detectors: Secondary Electrons (SE) Back Scattered Electrons (BSE, 5 segments) Energy dispersive X-Ray Analysis (EDS)
  • the acrylic foil used in accordance with the invention is preferably produced by means of a coextrusion process.
  • a coextruded acrylic foil is substantially free of volatile organic compounds such as solvents, which is highly advantageous for toxicological and environmental reasons.
  • the individual components of the layers A and B of the coextruded acrylic foil can be blended before or even during the extrusion step.
  • a line having at least the following components can be used:
  • a hot melt is extruded from the die of the extruder onto a nip between two polishing rolls or onto a chill roll.
  • the optimum melt temperature is dependent, for example, on the composition of the mixture and may therefore vary within wide ranges.
  • Preferred temperatures of the moulding composition up to the point of die entry are in the range from 170 °C to 320 °C, more preferably in the range from 200 °C to 290 °C and very preferably in the range from 220 °C to 280 °C.
  • the temperature of the polishing rolls is preferably less than or equal to 150 °C, more preferably between 60 °C and 140 °C.
  • the temperature of the die is higher than the temperature of the mixture prior to die entry.
  • the die temperature is preferably set 10 °C, more preferably 20 °C and very preferably 30 °C higher than the temperature of the mixture prior to die entry. Accordingly, preferred temperatures of the die are in the range from 160 °C to 330 °C, more preferably 190 °C to 300 °C.
  • the polishing stack may consist of two or three polishing rolls. Polishing rolls are widely known in the art and are used to obtain a high gloss. Nevertheless, rolls other than polishing rolls e.g. matt rolls can also be used in the method of the invention. The nip between the first two polishing rolls forms a sheet which becomes a foil by virtue of the simultaneous cooling.
  • the sheet of melt may be deposited onto a single cooled roll, which transports it further. Chill rolls are preferably located over the polishing stacks.
  • the extrusion can be carried out in a particularly advantageous way using equipment described in patent applications US 2016/015 9995 A1 and US 2017/030 6188 A1 , the entire disclosure of which is incorporated herein by reference.
  • Particularly good surface quality of the foil can be ensured by the die and roll having chrome surfaces, and especially by these chrome surfaces having a roughness Ra (according to DIN 4768 (1990)) of less than 0.10 ⁇ m, preferably less than 0.08 ⁇ m.
  • a filter may be optionally located before the entry of the melt into the die.
  • the mesh size of the filter is guided generally by the starting materials used, and may therefore vary within wide ranges. Mesh sizes generally are in the range from 300 ⁇ m to 20 ⁇ m. Filters having two or more screens of different mesh size may also be located before the point of die entry. These filters are available commercially. To obtain foils of high quality, it is advantageous, moreover, to use particularly pure raw materials.
  • a static mixing element may be installed upstream of the flat foil die.
  • This mixing element can be used to mix components such as colourants, stabilizers or additives into the polymer melt, or up to 5 wt% of a second polymer, for example in the form of a melt, may be mixed from a second extruder into the material.
  • the pressure with which the melted mixture is pressed into the die may be controlled, for example, via the speed of the screw.
  • the pressure is typically within a range of from 40 bar to 300 bar, without this limiting the method of the invention. Accordingly, the speed with which the foils can be obtained in accordance with the invention is generally greater than 5 m/min, more particularly greater than 10 m/min.
  • a melt pump may additionally be installed upstream of the flat foil die.
  • a liner layer 10 is bound to the coextruded acrylic foil 4 from the step i) downstream of the extruder at a temperature below the glass transition temperature of the employed acrylic polymers, whereby a laminate 11 is obtained.
  • the resulting laminate 11 will typically consist of the following two layers (cf. Fig. 3 ):
  • the liner layer 10 is self-adhesive.
  • the liner layer 10 may have an adhesive layer and can be advantageously used for binding the liner layer 10 to a coextruded acrylic foil 4 having a matt surface.
  • the liner layer 10 may have a layer of a polyethylene-copolymer instead of an adhesive layer.
  • Such liners are advantageously employed for coextruded acrylic foils 4 having a glossy surface.
  • the liner layer 10 preferably has an initial tear resistance, measured according to ASTM D1004 (2013 ), of from 50 N to 500 N.
  • the material of the liner layer 10 is not particularly limited, as long as the liner layer 10 has a sufficient tear resistance and can be selected from one of the following: polyethylene, polypropylene, polyimide, polyethylene terephthalate and polyethylene naphthalate, preferably a biaxially oriented polypropylene or a biaxially oriented polyethylene terephthalate or mixtures thereof, whereby a biaxially oriented polypropylene or a biaxially oriented polyethylene terephthalate are particularly preferred.
  • the laminate 11 will undergo a step of binding an adhesive layer 7 , optionally, a release coating layer 8 and a support layer 9 to deliver a label stock 12 ( Fig. 3 ).
  • adhesive layer 7 optionally, a release coating layer 8 and a support layer 9 to deliver a label stock 12 ( Fig. 3 ).
  • the process comprising at least the following steps:
  • the laminate 11 obtained in step ii) can be passed between a plurality of rolls, wherein at least a roll facing towards the side of the coextruded acrylic foil 4 is a cooled roll.
  • the process may comprise at least the following steps:
  • the adhesive layer 7 substantially consists of a pressure sensitive adhesive (PSA).
  • PSA pressure sensitive adhesive
  • the support layer typically comprises a paper or plastic foil material and may be coated by a release coating layer 8.
  • release coating layer 8 Various release coating compositions are known such as those described US 6,406,787 .
  • Non-PSA adhesive compositions may also be used particularly for embodiments wherein the form support layer is porous ( e.g. paper), the form substrate being exposed on the non-viewing surface of the label.
  • PSAs suitable in the present invention are preferably selected from the group consisting of alkylacrylate polymers and copolymers; copolymers of alkylacrylates with acrylic acid; terpolymers of alkylacrylates, acrylic acid, and vinyl-lactates; alkyl vinyl ether polymers and copolymers; polyisoalkylenes; polyalkyldienes; alkyldiene-styrene copolymers; styrene-isoprene-styrene block copolymers; polydialkylsiloxanes; polyalkylphenylsiloxanes; natural rubbers; synthetic rubbers; chlorinated rubbers; latex crepe; rosin; cumarone resins; alkyd polymers; and polyacrylate esters and mixtures thereof.
  • Examples include polyisobutylenes, polybutadienes, or butadiene-styrene copolymers, and mixtures thereof (such polymers and copolymers preferably have no reactive moieties, i.e. are not oxidized in the presence of air); silicone-based compounds such as polydimethylsiloxane, and polymethylphenylsiloxane combined with other resins and/or oils.
  • PSAs also include tackified thermoplastic resins and tackified thermoplastic elastomers, wherein the tackifier comprises one or more compounds which increases the tack of the composition.
  • a tackified thermoplastic resin useful as an aggressively PSA is the combination of a vinyl acetate/ethylene copolymer known under the trade designation VYNATHENE EY 902-30 (available from Quantum Chemicals, Cincinnati, Ohio) with substantially equal portions of the tackifiers known under the trade designations PICCOTEX LC (a water-white thermoplastic resin produced by copolymerization of vinyltoluene and alpha-methylstyrene monomers having a ring and ball softening point of about 87°C to 95°C, available from Hercules Incorporated, Wilmington, Del.) and WINGTACK 10 (a liquid aliphatic C-5 petroleum hydrocarbon resin available from Goodyear Chemical) and an organic solvent such as toluene.
  • thermoplastic elastomer useful as an aggressively PSA is the combination of the styrene-poly(ethylene-butylene)-styrene block copolymer known under the trade designation KRATON G1657 (available from of Shell Chemicals) with one or more of the low molecular weight hydrocarbon resins known under the trade designation REGALREZ (from Hercules) and an organic solvent such as toluene. Both of these formulations may be coated using a knife coater and air-dried, or air-dried followed by oven drying. Of course, the invention is not limited to use of these specific combinations of thermoplastic resins, thermoplastic elastomers, and tackifiers.
  • Some presently preferred PSAs exhibit extended shelf life and resistance to detackifying under atmospheric conditions, and include acrylic-based copolymer adhesives as disclosed in U.S. Pat. No. Re 24,906 .
  • acrylic-based copolymer adhesives as disclosed in U.S. Pat. No. Re 24,906 .
  • One example of such an acrylic-based copolymer is a 95.5 : 4.5 (measured in parts by weight of each) isooctylacrylate/acrylic acid copolymer.
  • Another preferred adhesive is the copolymer of a 90 : 10 weight ratio combination of these two monomers.
  • Yet other preferred adhesives are terpolymers of ethyl acrylate, butyl acrylate, and acrylic acid; copolymers of isooctylacrylate and acrylamide; and terpolyrmers of isooctylacrylate, vinyl-acetate, and acrylic acid.
  • Acrylic-based PSAs can be coated out of a coatable composition comprising an organic solvent, such as a heptane : isopropanol solvent mixture, and the solvent subsequently evaporated, leaving a pressure-sensitive adhesive coating.
  • This layer is preferably from about 0.038 centimeters (cm) to about 0.11 cm (5 to 15 mils) thick when the substrate is a retroreflective sheeting material.
  • PSAs useful in the invention also may be characterized by having 180° peel adhesion ranging from about 10 to about 1000 g/cm, more preferably at least about 50 g/cm.
  • the 180° peel adhesion typically ranges from about 200 g/cm to about 600 g/cm, measured using a standard test procedure. In this procedure, the force necessary to remove (i.e. peel) a PSA-coated substrate from a test substrate when the PSA-coated substrate is peeled from the test substrate is termed the " peel adhesion " value.
  • a standard glass plate is cleaned using a solvent (such as one wash of diacetone alcohol followed by three washes of n-heptane).
  • a sample having a PSA-backsize coating is then applied along the center of the standard glass plate, PSA side down.
  • the sample is then rolled once with a 2.04 kg hand roller.
  • the standard glass plate is then secured to a horizontal plate in a standard peel adhesion tester such as that known under the trade name "IMASS.”
  • One end of the sample is then attached to a hook which is a part of the peel adhesion tester.
  • the sample is peeled from the standard glass plate at a 180° angle (i.e ., one end of the sample is pulled toward the other end) by moving the platen horizontally at a speed of 228.6 cm/min, and the force required recorded, in g/cm of sample width, for various dwell times.
  • the release coating layer 8 which is typically a siloxane coating, serves the purpose of reducing the adhesion between the adhesive layer 7 and the support layer 9.
  • the release coating layer 8 allows to achieve a kinetic coefficient of friction below 0.35, preferably below 0.25, determined according to the norm ASTM D1894 (2014).
  • the label stock 1 will undergo a kiss cutting to form a plurality of individual self-adhesive laser engravable labels 2 bound to a support layer 9.
  • the kiss cutting may be performed by means of a mechanical die cutting as described in US 2011/0132522 A1 or by using a laser.
  • the waste matrix 3 surrounding the individual self-adhesive laser engravable labels 2 will be peeled off from the support layer 9 without any risk of rupture.
  • the distance between individual labels i.e. the width of the stripes in the waste matrix
  • the distance between individual labels is kept in the range of from 1.0 mm to 10.0 mm, more preferably from 2.0 mm to 8.0 mm, even more preferably from 3.0 mm to 5.0 mm.
  • the release force during this operation is below 30 g/inch, preferably below 20 g/inch, even more preferably from 1 g/inch to 10 g/inch, measured using T-peel test with a tesaband ® 7475 tape from tesa SE (Norderstedt, Germany).
  • Laser engravable label 2 of the present invention comprise at least the following layers in the order stated ( cf. Fig. 2 ):
  • the laser engravable label the present invention has a thickness of between 50.0 ⁇ m and 300.0 ⁇ m, more preferably between 100.0 ⁇ m and 200.0 ⁇ m.
  • the size of the laser engravable labels can in principle be freely selected and is only limited by the dimension extrusion die and/or the polishing stack used for their production. This means that the formats are substantially freely selectable.
  • the trimming and kiss cutting of the coextruded acrylic foil is preferably accomplished by means of die cutting, cutting, laser cutting or laser die cutting. Particular preference is given to laser cutting or laser die cutting.
  • the coextruded acrylic foils produced in accordance with the invention may be provided additionally with ridges, cuts, slits or perforation or notches in order to additionally facilitate destruction of the labels during an attempt of their non-authorised removal.
  • additional means are not essential.
  • the laser engravable labels are highly suitable for producing electronic product identification label, automotive under-the-hood label, chip cards, heat resistant documents and seals.
  • One illustrative example of the use is that, for example, barcode labels on various parts of an automotive engine.
  • the labels can withstand operating temperatures of the engine without any noticeable shrinkage and are also chemically resistant to fluids such as brake fluid, hydraulic fluid, engine oil etc.
  • the label will become destroyed upon an unauthorised attempt to peel it off from an engine part in order to transfer it to a replaceable non-genuine engine part.
  • the labels of the present invention can bear a vehicle identification number and can be advantageously used under the hood of a vehicle. An unauthorised attempt to remove the label from a vehicle in order to attach it to a different vehicle will result in label destruction.
  • the foils comprising layers A and B were produced by adapter co-extrusion using chill-roll process at the extrusion speed of 7.3 m/min using a 35 mm-diameter single screw extruder and a 25 mm-diameter single screw co-extruder from Dr. Collin GmbH (Ebersberg, Germany) under the following conditions:
  • foils can be achieved by way of a multiple-manifold co-extrusion process or a combination of adapter and multiple-manifold co-extrusion.
  • the pigment used in the layer A was carbon black FW1 (Pigment Black 7), available from The Cary Company, Addison, USA.
  • Acrylic polymer 1 mentioned in examples below was PMMI PLEXIMID ® TT50, available from Röhm GmbH, Darmstadt, Germany.
  • Acrylic polymer 2 mentioned in the examples below was a copolymer of 99 wt.-% methyl methacrylate and 1 wt.-% methyl acrylate with mass average molecular weight Mw of 110 000 g/mol (determined by means of GPC against a PMMA standard), available from Röhm GmbH, Darmstadt, Germany.
  • Acrylic polymer 3 mentioned in the examples below was a copolymer of 96 wt.-% methyl methacrylate and 4 wt.-% methyl acrylate with mass average molecular weight Mw of 155 000 g/mol (determined by means of GPC against a PMMA standard), available from Röhm GmbH, Darmstadt, Germany.
  • Acrylic polymer 4 mentioned in the examples below was a copolymer of 75 wt.-% of MMA, 15 wt.-% of styrene and 10 wt.-% of maleic anhydride.
  • the weight-average molar mass Mw of this copolymer was about 140 000 g/mol (determined by means of GPC against a PMMA standard).
  • Impact modifier 1 was ACRYPET TM IR 441, available from Mitsubishi Chemical Co, Japan.
  • Impact modifier 2 was Paraloid TM EXL-2688, available from Dow Chemical Co, United States.
  • Impact modifier 3 was a butylacrylat-based acrylic core-shell-shell impact modifier.
  • the foil can be used for the manufacturing of self-adhesive laser engravable labels. No undesired rupture of the waste matrix takes place.
  • composition and layer thickness of foils of Examples 1-25 is summarised in Table 1 below: Table 1.
  • Composition and layer thickness of foils of Examples 1-25 Layer A Layer B Acrylic polymer, wt.-% Impact modifier, wt.-% Pigment, wt.-% Layer thickness Acrylic polymer, wt.-% Impact modifier, wt.-% Filler, wt.-% Layer thickness Ex. 1 polymer 1, 85.0 % modifier 1, 10.0% 5.0% 15 ⁇ m polymer 1, 55.0 % modifier 1, 25.0% 20.0% 45 ⁇ m
  • Table 1 Composition and layer thickness of foils of Examples 1-25
  • Layer A Layer B Acrylic polymer, wt.-% Impact modifier, wt.-% Pigment, wt.-% Layer thickness Acrylic polymer, wt.-% Impact modifier, wt.-% Filler,
  • Initial tear resistance was measured according to ASTM D 1004/ -/ 51 (2013 ) at 51 mm/min (initial grip separation 25.4mm).
  • the normed tear resistance was calculated by dividing the initial tear resistance with the thickness of the specimen, therefore small differences in thickness are ruled out, to make samples more comparable.
  • Example 5 and 6 comprised no impact modifiers in one of both layers and therefore illustrate the teaching of WO 2019/057645 A1 . These foils were found to be highly brittle and, because of a difficult handling, they were not suitable for manufacturing on an industrial scale.
  • foils of the present invention had an advantageous combination of mechanical properties for use a laser engravable label.
  • Table 2 Mechanical properties of foils of Examples 1-25 Initial tear resistance, N Normed tear resistance, N/mm Average tear propagation force, N Tear initiation force, N Maximal tear propagation force, N Tensile strength, MPa Elongation at break, % Ex. 1 3.6 55.2 51.3 11.00% Ex. 2 4.3 69.7 50.3 14.60% Ex. 3 7.3 116.5 0.04 0.01 0.07 53.7 5.10% Ex. 4 11.3 162.5 0.09 0.01 0.12 50.1 26.20% Ex. 5* 0 0 29.1 3.40% Ex. 6* 0 0 30.8 0.95% Ex.
  • the shrinkage of the samples was measured at 120 °C, 130 °C, 140 °C, 150 °C and 160 °C (60 minutes) according to standard DIN 53377 (2015) in extrusion direction and transverse direction. Materials having a high shrinkage at increased temperatures are usually not suitable for labelling parts of a vehicle which can reach such temperature.
  • Foils of Examples 1 and 2 comprised PMMI as acrylic polymer in layers A and B and therefore, as expected, had a rather low shrinkage in extrusion direction, even at a temperature of 160 °C.
  • Foils of Examples 11 and 12 comprised a blend of polymethyl methacrylates with a relatively low heat resistance in both layers. Therefore, these foils had a high shrinkage at temperatures above or at 130 °C.
  • Foils of Examples 5, 6, 7 and 23 comprised a copolymer of MMA, styrene and maleic anhydride. This material had a relatively high heat resistance so that the foils had a low shrinkage at temperatures below 140 °C. At a higher temperature a considerable shrinkage in extrusion direction took place.
  • the foils of Examples 16-19 comprised PMMI in one of both layers, the other layer comprising polymethyl methacrylates having a low heat resistance. Surprisingly, presence of PMMI in only one or both layers was sufficient to ensure that the foils had only a moderate shrinkage at increased temperatures.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Cosmetics (AREA)
EP20203881.6A 2020-10-26 2020-10-26 Étiquettes gravables au laser Pending EP3988294A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP20203881.6A EP3988294A1 (fr) 2020-10-26 2020-10-26 Étiquettes gravables au laser
KR1020237017628A KR20230093042A (ko) 2020-10-26 2021-10-21 레이저 각인 가능 라벨
CN202180072822.9A CN116390853A (zh) 2020-10-26 2021-10-21 可激光雕刻标签
JP2023525072A JP2023547629A (ja) 2020-10-26 2021-10-21 レーザー彫刻可能なラベル
IL302251A IL302251A (en) 2020-10-26 2021-10-21 Labels for laser engraving
PCT/EP2021/079197 WO2022090048A1 (fr) 2020-10-26 2021-10-21 Étiquettes pouvant être gravées au laser
EP21791423.3A EP4232276A1 (fr) 2020-10-26 2021-10-21 Étiquettes pouvant être gravées au laser
US18/249,483 US20230391057A1 (en) 2020-10-26 2021-10-21 Laser engravable labels

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CN (1) CN116390853A (fr)
IL (1) IL302251A (fr)
WO (1) WO2022090048A1 (fr)

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USRE24906E (en) 1955-11-18 1960-12-13 Pressure-sensitive adhesive sheet material
DE8130861U1 (de) 1981-10-22 Beiersdorf Ag, 2000 Hamburg Mehrschichtiges Etikett
EP0113924A2 (fr) 1983-01-10 1984-07-25 Röhm Gmbh Agent de modification de la résistance à l'impact
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US2146209A (en) 1936-07-31 1939-02-07 Du Pont Preparation of resinous imides of substituted acrylic acids
USRE24906E (en) 1955-11-18 1960-12-13 Pressure-sensitive adhesive sheet material
EP0113924A2 (fr) 1983-01-10 1984-07-25 Röhm Gmbh Agent de modification de la résistance à l'impact
EP0216505A2 (fr) 1985-08-27 1987-04-01 Rohm And Haas Company Polyimides, préparation de polyimides et compositions de polyimides
EP0441148A2 (fr) 1990-02-01 1991-08-14 Röhm Gmbh Procédé d'imidisation de polymères d'esters méthacryliques
EP0465049A2 (fr) 1990-07-03 1992-01-08 Rohm And Haas Company Matières plastiques claires résistant aux chocs
EP0522351A1 (fr) 1991-06-29 1993-01-13 Röhm Gmbh Agent pour la modification de la résistance à l'impact
EP0666161A2 (fr) 1994-01-29 1995-08-09 Röhm GmbH Procédé de traitement de coute durée de matière thermoplastique en fusion avec un agent de traitement et matière thermoplastique obtenué
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DE10142638A1 (de) 2001-08-31 2003-05-08 Tesa Ag Verfahren zum Herstellen einer laserbeschriftbaren Folie
US20040091657A1 (en) 2002-11-13 2004-05-13 3M Innovative Properties Company Method of making printable forms comprising stickers and articles
US20110132522A1 (en) 2008-07-14 2011-06-09 Avery Dennison Corporation Apparatus and Process for Cutting Adhesive Labels
WO2014035608A1 (fr) 2012-08-29 2014-03-06 Dow Global Technologies Llc Composition de polymère multicouche et films formés à partir de celle-ci
US20160159995A1 (en) 2013-07-10 2016-06-09 Riken Technos Corporation Poly(meth)acrylimide film, easy-adhesion film using same, and method for manufacturing such films
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JP2017111344A (ja) 2015-12-17 2017-06-22 リンテック株式会社 脆質性レーザマーカラベルの製造方法
EP3450163A1 (fr) * 2017-08-30 2019-03-06 Evonik Röhm GmbH Films acryliques fragiles et étiquettes de prévention de contrefaçon les comprenant
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EP4232276A1 (fr) 2023-08-30
JP2023547629A (ja) 2023-11-13
US20230391057A1 (en) 2023-12-07
CN116390853A (zh) 2023-07-04
WO2022090048A1 (fr) 2022-05-05
IL302251A (en) 2023-06-01
KR20230093042A (ko) 2023-06-26

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